Bis (Salicylaldiminato) titanium complex catalysts, highly syndiotactic polypropylene by a chain-end control mechanism, block copolymer containing this

ABSTRACT

Bis(salicylaldiminato)titanium complex with optionally substituted phenyl or cyclohexyl on nitrogen catalyzes highly syndiospecific polymerization of propylene. Syndiotactic polypropylene with defects of the type rmr having [rrrr] content greater than 0.70 and block copolymer containing block(s) of the syndiotactic polypropylene and block(s) of poly(ethylene-co-propylene) and/or poly(alpha-olefin-co-propylene) are obtained. Certain of the catalysts provide living polymerization. Living olefin polymers and olefin terminated oligomers and polymers are also products.

[0001] The invention was made at least in part with United StatesGovernment support under National Science Foundation related grant CCMR(Cornell Center for Materials Research) Grant Number DMR 0079992. TheUnited States Government has certain tights in the invention.

TECHNICAL FIELD

[0002] This invention is directed to bis(salicylaldiminato)titaniumcomplex catalysts, and highly syndiotactic polypropylene makabletherewith by a chain-end control mechanism, and block copolymerscontaining the syndiotactic polypropylene andpoly(ethylene-co-propylene) and/or poly(alpha-olefin-co-propylene), aswell as to living olefin polymers and to olefin terminated oligomers andpolymers and to methods of making syndiotactic polypropylene, blockcopolymers and olefin-terminated oligomers and polymers from propylene.

BACKGROUND OF THE INVENTION

[0003] The kind of polypropylene in general use, for example, forpackaging and container functionality, is isotactic polypropylene. It istypically described as having the methyl groups attached to the tertiarycarbon atoms of successive monomeric units on the same side of ahypothetical plane through the main chain of the polymer. Isotacticpolypropylene lacks clarity and thus is not useful in cases where thisis important.

[0004] Another kind of polypropylene is syndiotactic polypropylene. Itmay be described as having the methyl groups attached to the tertiarycarbon of successive monomeric units on alternate sides of ahypothetical plane through the main chain of the polymer. Syndiotacticpolypropylene is clear, that is it does not have the lack of claritycharacteristic of isotactic polypropylene.

[0005] There are two types of syndiotactic polypropylene. One of thesetypes is referred to as being made by a chain-end control mechanism andcontains defects of the rmr type. NMR analysis for this kind ofstructure is shown in Zambelli, et al., Macromolecules, 13, 267-270(1980). The most syndiospecific polypropylene of this type made beforethis invention has [rrrr] pentad content of 0.63 (described inPellecchia, C., et al., Macromol. Rapid Commun. 17,333-338 (1996)) whichlimits the usage since the lower the [rrrr] pentad content, the lowerthe melting point. For example, a container made from polypropylene with[rrrr] pentad content of 0.63 will melt on contact with boiling waterand thus is unuseful for containers for hot liquids. We turn now to theother type of syndiotactic polypropylene. It is referred to as beingmade by a site-control mechanism and as containing defects of the rmmrtype. This type of polypropylene is described in European PatentApplication Publication 0351391 A2 (published Jan. 17, 1990). Highlysyndiotactic polypropylene ([rrrr]=0.97) has been made by a site-controlmechanism See Ewen, J. A., et al., J. Am. Chem. Soc., 110, 6255-6256(1988), Herzog, T. A., et al., J. Am. Chem. Soc. 118, 11988-11989(1996), and Veghini D., et al., J. Am. Chem. Soc. 121, 564-573 (1999).This kind of syndiotactic polypropylene has not yet been commercializedapparently because of processing and/or economic factors.

SUMMARY OF THE INVENTION

[0006] It has been discovered herein that highly syndiospecificpolypropylene can be made by a chain-control mechanism by utilizingcertain bis(salicylaldiminato)titanium complex compounds as catalysts aswell as block copolymers containing block(s) of the syndiotacticpolypropylene and block(s) of poly(ethylene-co-propylene) and/orpoly(alpha-olefin-co-propylene) and that living polymerization can beobtained and that certain of the catalysts are useful in the productionof olefin terminated polymers and oligomers from propylene.

[0007] The invention herein in one embodiment, denoted the firstembodiment, is directed to a bis(salicylaldiminato)titanium complexhaving the structure:

[0008] where R is selected from the group consisting of halogen atoms,C₁-C₁₀ branched or straight chain alkyl groups, C₁-C₆ branched orstraight chain alkoxide groups, and C₁-C₆ branched or straight chainamido groups, R₁ is phenyl substituted with C₁-C₆ branched or straightchain alkyl group or electron withdrawing atom or group at the2-position and optionally substituted with C₁-C₆ branched or straightchain alkyl groups or electron withdrawing atom or group at one or moreof the 3-, 4-, 5- and 6-positions, or is C₁-C₁₀ branched, cyclic orstraight chain alkyl group, and R₂ and R₃ are the same or different andare selected from the group consisting of C₄-C₆ tertiary alkyl groups;or cationic form thereof. The complexes are useful as catalysts forpolymerization of olefins and are especially useful for polymerizationof propylene.

[0009] The invention herein in another embodiment, denoted the secondembodiment, is directed to syndiotactic polypropylene having M_(w)ranging from 10,000 to 500,000 and defects of the type rmr and [rrrr]pentad content greater than 0.70. The syndiotactic polypropylene isuseful, for example, for packaging and container functionality.

[0010] The invention herein in another embodiment, denoted the thirdembodiment, is directed to syndiotactic poly(C₄-C₆-alpha olefins) havinga M_(w) ranging from 10,000 to 500,000 and M_(w)/M_(n) ranging from 1.0to 2.0. These syndiotactic polyolefins are useful for films and sheetsbecause of their flexibility and transparency.

[0011] The invention herein in another embodiment, denoted the fourthembodiment, is directed to a method of preparing syndiotacticpolypropylene having M_(w) ranging from 10,000 to 500,000 and defects ofthe type rmr and [rrrr] pentad content greater than 0.50 comprisingpolymerizing propylene dissolved in an aprotic solvent in the presenceof a catalytically effective amount of a complex having the structure:

[0012] where R is selected from the group consisting of halogen atoms,C₁-C₁₀ branched or straight chain alkyl groups, C₁-C₆ branched orstraight chain alkoxide groups, and C₁-C₆ branched or straight chainamido groups, R₁ is phenyl optionally substituted with one to five C₁-C₆branched or straight chain alkyl groups or one to five electronwithdrawing atoms or groups, or is C₁-C₁₀ branched, cyclic or straightchain alkyl group, and R₂ and R₃ are the same or different and areselected from the group consisting of H or C₁-C₆ branched or straightchain alkyl group, and an activating effective amount of compound thatconverts titanium of the complex to cationic form. The syndiotacticpolypropylene product has packaging and container functionality.

[0013] The invention herein in still another embodiment, denoted thefifth embodiment, is directed to olefin terminated polymers andoligomers of propylene having the structure:

[0014] where n ranges from 1 to 750. These compounds are useful, forexample, to add as so-called ‘macromonomers’ to other polymerizationsand can be incorporated about as well as hexene.

[0015] The invention in another embodiment denoted the sixth embodimentis directed to a method of preparing polymers and oligomers of propylenehaving the structure (II) where n ranges from 1 to 750 comprisingpolymerizing propylene in an aprotic solvent in the presence of acatalytically effective amount of complex having the structure (I) whereR is selected from the group consisting of halogen atoms, C₁-C₁₀branched or straight chain alkyl groups, C₁-C₆ branched or straightchain alkoxide groups, and C₁-C₆ branched or straight chain amidogroups, R₁ is phenyl optionally substituted at one or more of the 3-,4-, and 5-positions but not at the 2- and 6-positions, the optionalsubstitution at one or more of the 3-, 4- and 5-positions being withC₁-C₆ branched or straight chain alkyl group or electron withdrawingatom or group, and R₂ and R₃ are the same or different and are selectedfrom the group consisting of H and C₁-C₆ branched or straight chainalkyl groups and an activating effective amount of compound thatconverts titanium of the complex to cationic form, and quenching thereaction when olefin-terminated polymer or oligomer of desired number ofmonomer units is formed.

[0016] The invention herein in still another embodiment, denoted theseventh embodiment, is directed to block copolymer having M_(w) rangingfrom 10,000 to 500,000 comprising at least one block of syndiotacticpolypropylene and at least one block of poly(ethylene/propylene) wherethe ethylene content ranges from 1 to 100% by weight, containing avolume fraction of syndiotactic polypropylene ranging from 0.20 to 0.99.Species include block copolymer consisting essentially of one block ofsyndiotactic polypropylene and one block of poly(ethylene-co-propylene),block copolymer consisting essentially of a block of syndiotacticpolypropylene followed by a block of poly(ethylene-co-propylene)followed by a block of syndiotactic polypropylene, and block copolymerconsisting essentially of a block of syndiotactic polypropylene followedby a block of poly(ethylene-co-propylene) followed by a block ofsyndiotactic polypropylene followed by a block ofpoly(ethylene-co-propylene) followed by a block of syndiotacticpolypropylene.

[0017] The invention in still another embodiment, denoted the eighthembodiment is directed to block copolymer having M_(w) ranging from10,000 to 500,000 comprising at least one block of syndiotacticpolypropylene and at least one block of poly(alpha-olefin/propylene),e.g., poly(C₄-C₆ alpha-olefin/propylene), e.g., poly(1-butene/propylene)where the alpha-olefin content (not propylene) ranges from 1 to 100% byweight, containing a volume fraction of syndiotactic polypropyleneranging from 0.20 to 0.99.

[0018] Chain-end control and defects of the type rmr as referred toherein are described in Coates, G. W., Chem. Rev. 100, 1223-1252 (2000).

[0019] The [rrrr] pentad contents described herein are measured asdescribed in Resconi L., et al., Chem. Rev. 100, 1253-1345 (2000).

[0020] The term “electron withdrawing atom or group” is used herein tomean atom or group where the connecting atom of the atom or group ismore electronegative than hydrogen.

[0021] The term “M_(w)” is used herein to mean weight average molecularweight, and the term “M_(n)” is used herein to mean number averagemolecular weight and these are determined using gel permeationchromatography (GPC) in 1,2,4-trichlorobenzene at 140° C. versuspolystyrene standards, unless otherwise stated.

DETAILED DESCRIPTION

[0022] We turn now to the first embodiment of the invention which isdirected to a bis(salicylaldiminato)titanium complex having thestructure:

[0023] where R is selected from the group consisting of halogen atoms,C₁-C₁₀ branched or straight chain alkyl groups, C₁-C₆ branched orstraight chain alkoxide groups and C₁-C₆ branched or straight chainamido groups, R₁ is phenyl substituted with C₁-C₆ branched or straightchain alkyl group or electron withdrawing group at the 2-position andoptionally substituted with C₁-C₆ branched or straight chain alkyl groupor electron withdrawing atom or group at one or more of the 3-, 4-, 5-and 6-positions, or is C₁-C₁₀ branched, cyclic or straight chain alkylgroup, and R₂ and R₃ are the same or different and are selected from thegroup consisting of C₄-C₆ tertiary alkyl groups; or cationic formthereof.

[0024] R is described in conjunction with formula (I) as being selectedfrom the group consisting of halogen atoms, C₁-C₁₀ branched or straightchain alkyl groups and C₁-C₆ branched or straight chain alkoxide groupsand C₁-C₆ branched or straight chain amido groups. The halogen atomsinclude, for example, chlorine, fluorine and bromine atoms. The C₁-C₆branched or straight chain alkyl groups include, for example t-butylgroups. In the compounds synthesized in the working examples, R is achlorine atom.

[0025] R₁ is described in conjunction with formula (I) as being phenylsubstituted with C₁-C₆ branched or straight chain alkyl group orelectron withdrawing atom or group at the 2-position and optionallysubstituted with C₁-C₆ branched or straight chain alkyl group orelectron withdrawing atom or group at one or more of the 3-, 4-, 5- and6-positions, or is C₁-C₁₀ branched, cyclic or straight chain alkylgroup. The C₁-C₆ branched or straight chain alkyl groups include, forexample, t-butyl. The electron withdrawing groups include, for example,fluorine atoms, nitro groups, trifluoromethyl groups, cyanide groups,and aldehyde groups. In Example X hereinafter, compounds of the formula(I) with R₁ being phenyl substituted at least at the 2-position withfluoro were found to catalyze living polymerization of propylene asshown by M_(w)/M_(n) in the range of 1.0 to 1.35, and compounds of theformula (I) with R₁ being phenyl substituted with fluoro at least at the2- and 6-positions were found to catalyze polymerization of propylene togive syndiotactic polypropylene with M_(w)/M_(n) in the range of 1.0 to1.35 and defects of the type rmr and [rrrr] pentad content greater than0.70. In Example X, compound of the formula (I) with R₁ being phenylsubstituted with fluoro at the 2-, 3-, 4-, 5- and 6-positions, was foundto catalyze polymerization of propylene to give syndiotacticpolypropylene with M_(w)/M_(n) in the range of 1.0 to 1.35, i.e., livingpolymerization, and defects of the type rmr and [rrrr] pentad content ofat least 0.95.

[0026] R₂ and R₃ are described in conjunction with formula (I) as beingthe same or different and as being selected from the group consisting ofC₄-C₆ tertiary alkyl groups. R₂ and R₃ being C₄-C₆ tertiary alkyl groupwas found to be advantageous in respect to catalyzing polymerization ofpropylene to give syndiotactic polypropylene compared to where one of R₂and R₃ is H in providing higher activity and higher M_(n) as indicatedby a comparison of results for A and H in Table II of Example Xhereinafter.

[0027] In several cases represented herein, the complexes have C-2symmetry, i.e., both R₁s are the same, both R₁s are the same, both R₂sare the same, and both R₃s are the same.

[0028] Cationic form of the complex is referred to. This is the formactive to catalyze polymerization. As indicated later, the complex canbe converted to cationic form by co-catalyst that converts titanium ofthe complex to cationic form, e.g., when R is chlorine, analuminum-containing co-catalyst can be used to pull off both chlorinesand convert one to methyl or where R is alkyl the co-catalyst[Ph₃C][B(C₆F₅)₄] can be used to abstract one alkyl.

[0029] Complexes of the formula (I) synthesized in the working exampleshave the structural formula:

[0030] where R₁, R₂ and R₃ are defined as in Table I below: TABLE IComplex R₁ R₂ R₃ A Ph ^(t)Bu ^(t)Bu B (4-^(t)Bu)Ph ^(t)Bu ^(t)Bu C^(c)C₆H₁₁ ^(t)Bu ^(t)Bu D (2-F)Ph ^(t)Bu ^(t)Bu E (2,6-F₂)Ph ^(t)Bu^(t)Bu F (2,4,6-F₃)Ph ^(t)Bu ^(t)Bu G (2,3,4,5,6-F₅)Ph ^(t)Bu ^(t)Bu H(3,5-F₂)Ph ^(t)Bu ^(t)Bu I Ph ^(t)Bu H

[0031] In Table 1, °C₆ H₁₁, means cyclohexyl.

[0032] Complexes D, E, F and G of Table I are embraced by the firstembodiment of the invention herein and complexes A, B, C, H and I arenot embraced by the first embodiment of the invention herein.

[0033] The complexes of the formula (I) can be synthesized by reactionof 3-R₂, 5-R₃-salicylaldehyde, e.g., 3,5-di-tert-butylsalicylaldehydewhere R₂ and R₃ are to be t-butyl and 3-tert-butylsalicylaldehyde whereR₂ is to be t-butyl and R₃ is to be H, with aniline or substitutedaniline or cyclohexylamine where the substituents provide thesubstituents on phenyl of R₁, e.g., 2-fluoroaniline where R₁ is to be2-fluorophenyl, to obtain a ligand, and reacting the ligand with Ti(R)₄,e.g., Ti(Cl)₄ where R is to be Cl, in the presence of n-butyllithium andthen isolating by crystallization. Where three or more fluorinesubstituents are on aniline reactant, the aniline reactant needs to beactivated by forming the N-sulfinyl derivative of the fluoroanilinewhich is then reacted with the 3-R₂, 5-R₃-salicylaldehyde, e.g.,N-sulfinyl-2,4,6-trifluoroaniline is used to obtain R₁ which is2,4,6-trifluorophenyl. The N-sulfinyl derivative is formed by refluxingthe fluoroaniline with thionyl chloride. Specific reactions are setforth in working examples I, II, III, IV, V, VI, VI, VIII and IX, laterherein.

[0034] In the above description of the first embodiment of theinvention, compounds of the formula (I) are said to catalyze livingpolymerization of propylene. This means that the more of the monomerthat is present, the longer the polymer obtained. The polymerizationcontinues in this fashion until reactant is used up or the reaction isquenched by knocking the metal of the catalyst from the end of thepolymer. The obtaining of living polymerization is shown by a lowM_(w)/M_(n), e.g., M_(w)/M_(n) ranging from 1.0 to 1.35. Livingpolymerization provides syndiotactic polypropylene without olefin endgroup.

[0035] We turn now to the second embodiment of the invention, which isdirected to syndiotactic polypropylene having M_(w) ranging from 10,000to 500,000 and defects of the type rmr and [rrrr] pentad content greaterthan 0.70. The polymer is made by a chain-end control mechanism sincedefects of the type rmr are recited. In one subgroup, the syndiotacticpolypropylene has [rrrr] pentad content of at least 0.95. In anothersubgroup which can be overlapping with the first subgroup, M_(w)/M_(n)ranges from 1.05 to 1.35 and in products made in working examples rangesfrom 1.06 to 1.34. The syndiotactic polypropylene of this embodiment ismade by the method of the fourth embodiment described below except thatcomplex D of Table 1 is excluded as the catalyst. Details of synthesisare presented in working Example X which is set forth later. It is notedthat some publications refer to [r] instead of [rrrr] pentad content;[r] to the fourth power gives [rrrr] pentad content for chain-endcontrol statistics. Synthesis of the syndiotactic polypropylene of thisembodiment can be carried out by the method of the fourth embodimentherein as described in conjunction with catalysis by complexes providing[rrrr] pentad content greater than 0.70.

[0036] We turn now to the third embodiment, which is directed tosyndiotactic poly(C₄-C₆-alpha-olefins) having a M_(w) ranging from10,000 to 500,000 and M_(w)/M_(n) ranging from 1.0 to 2.0, e.g., 1.0 to1.5. The polymers are made by a chain-end control mechanism when defectsof the type rmr are present. The alpha-olefins which are polymerized toprepare the syndiotactic poly(C₄-C₆ alpha-olefins) of this embodimentinclude, for example, 1-butene, 1-pentene, 1-hexene, and4-methyl-1-pentene. These polymers can be prepared by polymerizing thealpha-olefin in an aprotic solvent, e.g., toluene or hexanes, in thepresence of catalytically effective amount of complex of formula (I)where R is chlorine, R₁ is phenyl substituted with fluoro at least atthe 2- and 6-positions and R₂ and R₃ are t-butyl and an activatingeffective amount of compound that converts titanium of the complex tocationic form as described in conjunction with the fourth embodiment,preferably an aluminum-containing compound that converts titanium of thecomplex to cationic form The polymerization is appropriately carried outat 0° C. Aluminum-containing activator compounds include, for example,methyl aluminoxane (MAO) and polymethyl aluminoxane (PMAO) (which ismore soluble than methyl aluminoxane in the aprotic solvent and thusmore readily stays in solution). The amount of complex of formula (I)ranges from 0.2 to 20 mmol per 1,000 ml of solution of olefin on anolefin saturated solution basis. The aluminum-containing compoundactivator is used in a [Al]/[Ti] (the Ti being the Ti in the complex offormula (I)) ratio ranging from 10 to 1,000.

[0037] We turn now to the fourth embodiment of the invention, which isdirected to a method of preparing syndiotactic polypropylene having aM_(w) ranging from 10,000 to 500,000 and defects of the type rmr and[rrrr] pentad content greater than 0.50 comprising polymerizingpropylene dissolved in an aprotic solvent (preferably as a saturatedsolution) in the presence of a catalytically effective amount ofcomplex:

[0038] where R is selected from the group consisting of halogen atoms,C₁-C₁₀ branched or straight chain alkyl groups, C₁-C₆ branched orstraight chain alkoxide groups, and C₁-C₆ branched or straight chainamido groups, R₁ is phenyl optionally substituted with one to five C₁-C₆branched or straight chain alkyl groups or one to five electronwithdrawing atoms or groups, or is C₁-C₁₀ branched, cyclic or straightchain alkyl group, and R₂ and R₃ are the same or different and areselected from the group consisting of H or C₁-C₆branched or straightchain alkyl groups, and an activating effective amount of compound thatconverts titanium of the complex to cationic form. The aprotic solventcan be, for example, toluene or hexanes, and is preferably toluene. Thecomplex can be prepared as described above and is used in an amount from0.2 to 20 mmol per 1,000 ml of solution of olefin (on an olefinsaturated solution basis). The compound that converts titanium of thecomplex to cationic form is, for example, an aluminum-containingcompound. When the complex used is one where both Rs are chlorine, thealuminum-containing compound functions by pulling both chlorines fromthe complex and converting one to methyl. Another compound that convertstitanium of the complex to cationic form is [Ph₃ C][B(C₆ F₅)]₄; whencomplex is used where both Rs are alkyl this co-catalyst abstracts onealkyl. A class of compounds that converts titanium of the complex tocationic form are clays. An aluminum-containing compound for use toconvert titanium of the complex to cationic form preferably is methylaluminoxane (MAO), very preferably polymethyl aluminoxane (PMAO) whichis available from Akzo Nobel. The amount of aluminum-containing compoundused ranges from 10 to 1,000 on a [Al]/[Ti] basis. Reaction temperaturecan range, for example, from −20 to 100° C. and is preferably 0° C. andreaction times can range, e.g., from 1 hour to 50 hours. Syndiotacticpolypropylene with [rrrr] pentad content greater than 0.70 is obtainedusing complex of formula (I) as described above in conjunction with thisembodiment, except for complex D of Table I. Syndiotactic polypropylenewith M_(w)/M_(n) in the range of 1.0 to 1.3 5 and living polymerizationare obtained using complex of formula (I) as described above inconjunction with this embodiment where R₁ is phenyl substituted at leastat the 2-position with fluorine. The reaction can be carried out, forexample, at 01 to 300 psi and is carried out at 40 psi at 0° C. inExample X hereinafter. In living or other polymerization, thepolymerization can be ended when desired by knocking the metal of thecatalyst off the end of the product, e.g., by quenching by injection ofmethanol/HCl (10% by volume HCl) in amount of from 1 to 10 volumepercent of the polymerization solution.

[0039] We turn now to the fifth embodiment of the invention, which isdirected to olefin terminated polymers and oligomers of propylene havingthe structure:

[0040] where n ranges from 1 to 750. In the formula (II), n is thenumber of propylene units in the polymer or oligomer except for theolefin terminating end groups. Specific examples of this embodiment havethe formula (II), where n=1, 2, 3, 4, 10, 20, 50 or 100. These polymersand oligomers are prepared by a method comprising polymerizing propylenein a method which does not give living polymerization, e.g., in themethod of the sixth embodiment of the invention described below.

[0041] We turn now to the sixth embodiment of the invention which isdirected to a method of preparing polymers and oligomers of propylenehaving the structure (II) where n ranges from 1 to 750 comprisingpolymerizing propylene in an aprotic solvent, preferably as a saturatedsolution, in the presence of a catalytically effective amount of complexhaving the structure (I) where R is selected from the group consistingof halogen atoms, C₁-C₁₀ branched or straight chain alkyl groups, C₁-C₆branched or straight chain alkoxide groups, and C₁-C₆ branched orstraight chain amido groups, R₁ is phenyl optionally substituted at oneor more of the 3-, 4-, and 5-positions but not at the 2- and6-positions, the optional substitution at one or more of the 3-, 4- and5-positions being with C₁-C₆ branched or straight chain alkyl group orelectron withdrawing atom or group, and R₂ and R₃ are the same ordifferent and are selected from the group consisting of H and C₁-C₆branched or straight chain alkyl groups and an activating effectiveamount of compound that converts titanium of the complex to cationicform, and quenching the reaction when olefin-terminated polymer oroligomer of desired number of monomer units is formed.

[0042] The aprotic solvent can be, for example, toluene or hexanes andpreferably is toluene. The complex and synthesis thereof is describedabove. Suitable complexes for use in this embodiment include complexesA, H and I of Table I above. The amount of said complex which is acatalytically effective amount ranges from 0.2 to 20 mmol per 1,000 mlof solution of propylene (on a propylene saturated solution basis). Thecompound that converts titanium of the complex to cationic form is thesame as that described above in conjunction with the fourth embodimentof the invention herein. When the compound that converts titanium of thecomplex to cationic form is an aluminum-containing complex, it ispreferably MAO, very preferably PMAO, used in an activating effectiveamount, for example, from 10 to 1,000 on a [Al/Ti] basis. Reactiontemperature can range, for example, from −20 to 100° C. and preferablyis 0° C., and reaction time can range, for example, from 1 hour to 50hours. The reaction is quenched when desired amount of polymer isformed, e.g., by weighing solids in a sample and extrapolating to thewhole reaction.

[0043] We turn now to the seventh embodiment of the invention, which isdirected to block copolymer having M_(w) ranging from 10,000 to 500,000comprising at least one block of syndiotactic polypropylene and oneblock of poly(ethylene/propylene) where the ethylene content ranges from1 to 100% by weight, containing a volume fraction of syndiotacticpolypropylene ranging from 0.20 to 0.99. The syndiotactic polypropyleneis sometimes denoted SPP hereinafter. The poly(ethylene/propylene) ispolyethylene, sometimes denoted PE hereinafter, when the ethylenecontent of the poly(ethylene/propylene) is 100% and otherwise ispoly(ethylene-co-propylene), sometimes denoted EP hereinafter. Ingeneral the block polymers can be made by the methods for makingsyndiotactic polypropylene described hereinbefore but with sequentialaddition of monomers. The blocks of syndiotactic polypropylenepreferably have [rrrr] pentad content greater than 0.70.

[0044] In one species of the seventh embodiment, there is provided ablock copolymer having M_(w) ranging from 10,000 to 500,000 consistingessentially of one block of syndiotactic polypropylene and one block ofpoly(ethylene-co-propylene) where the volume fraction of syndiotacticpolypropylene ranges from 0.20 to 0.99. This block copolymer may bereferred to as a diblock. This block copolymer can be made as follows:The method for fourth embodiment is used initially where the complexused as catalyst is one that gives living polymerization, e.g.,complexes B, C, D, E, F and G in Table I. In the reaction, the aproticsolvent is preferably saturated with propylene gas under a pressureranging from 1 to 200, e.g., 40 psi. After the initial reaction wherebysyndiotactic polypropylene is produced, ethylene at an overpressure of 1to 10 psi compared to residual propylene pressure, is introduced andreaction proceeds to add a block of poly(ethylene-co-propylene). After adesired diblock is obtained, the reaction may be quenched, e.g., byinjection of methanol/10 volume percent HCl, and product is recovered byprecipitation and purification. Diblock of this type is made in ExampleX hereafter and is the 16th entry in Table II of Example X. The volumefraction of SPP in the diblock obtained in Example X was 0.26.

[0045] In a second species of the seventh embodiment, there is provideda block copolymer having a M_(w) ranging from 10,000 to 500,000consisting essentially of a block of syndiotactic polypropylene followedby a block of poly(ethylene-co-propylene) followed by a block ofsyndiotactic polypropylene, where the volume fraction of syndiotacticpolypropylene ranges from 0.20 to 0.99. This block copolymer may bereferred to as a triblock. This block copolymer can be made the same asthe diblock as described in the paragraph directly above, except thatafter the desired amount of formation of block ofpoly(ethylene-co-propylene), the ethylene feed is discontinued and thereaction consumes residual ethylene whereupon there is reversion topolymerization of propylene for the final block. Triblock of this typeis made in Example X in three runs as indicated by the seventeenth,eighteenth and nineteenth entries in Table II of Example X. The volumefraction of SPP in the triblock of the seventeenth entry of Table II was0.81 which gives a stiff characteristic. The volume fractions of SPP inthe triblocks of the eighteenth and nineteenth entries of Table II wererespectively 0.31 and 0.30 which provides an elastomeric regime sincethe EP block dominates.

[0046] In a third species of the seventh embodiment, there is provided ablock copolymer having a M_(w) ranging from 10,000 to 500,000 consistingessentially of a block of syndiotactic polypropylene followed by a blockof poly(ethylene-co-propylene) followed by a block of syndiotacticpolypropylene followed by a block of poly(ethylene-co-propylene)followed by a block of syndiotactic polypropylene, where the volumefraction of syndiotactic polypropylene ranges from 0.20 to 0.99. Thisblock copolymer may be referred to as a pentablock. This block copolymercan be made the same as the triblock as described in the paragraphdirectly above, except that the propylene polymerization is interruptedtwice by the addition of ethylene.

[0047] The block copolymers containing polyethylene block(s) can be madethe same as the block copolymers containing block(s) ofpoly(ethylene-co-propylene) as described above, except for the ethylenebeing introduced at higher pressure if propylene is present, e.g., 200psi so PE blocks are formed instead of EP blocks. Alternatively, thepropylene can be allowed to be consumed and the ethylene introduced atlow pressure, e.g., 5 psi. Structures made in this way include SPP-EP-PEtriblock, SPP-EP-PE-EP-SPP pentablock, PE-EP-SPP-EP-PE pentablock, andPE-EP-PE triblock.

[0048] We turn now to the eighth embodiment of the invention hereinwhich is directed to block copolymer having M_(w) ranging from 10,000 to500,000 comprising at least one block of syndiotactic polypropylene andat least one block of poly(alpha-olefin/propylene), e.g., poly(C₄-C₆alpha-olefin/propylene), e.g., poly(1-butene/propylene), where thealpha-olefin content (not propylene) ranges from 1 to 100% by weight,containing a volume fraction of syndiotactic polypropylene ranging from0.20 to 0.99. The term alpha-olefin is used in the description of thisembodiment to mean alpha-olefin different from propylene and ispreferably C₄-C₆-alpha-olefin and includes 1-butene, 1-pentene,1-hexene, and 4-methyl-1-pentene. In general the block copolymers can bemade by the methods for making syndiotactic polypropylene describedhereinbefore but with sequential addition of monomers, i.e., analogousto the way block copolymers of SPP and EP are made.

[0049] The invention is illustrated in and/or syntheses of catalysts foruse in preparing embodiments of the invention are illustrated in thefollowing working examples.

EXAMPLE I Synthesis of Complex A

[0050] To a 250 mL Schlenk tube, 20 mL of methanol, 1.860 g (20 mmol)aniline and 4.687 g (20 mmol) 3,5-di-tert-butylsalicylaldehyde wereintroduced, and then heated up to reflux for 8 h. Upon reducing thesolvent volume and cooling down afforded a bright brown crystals ofLigand A, which was isolated and dried under vacuum (5.882 g, 95%).¹H-NMR spectrum showed that it was the desired product.¹H NMR (CDCl₃,ppm, 20° C.): δ 1.32 (s, C(CH₃)₃, 9H), 1.47 (s, C(CH₃)₃9H), 7.18-7.30(m, Ar, 4H), 7.36-7.46 (m, Ar, 3H), 8.63 (s, CH, 1H). Ligand A (0.718 g,2 mmol) was dissolved in 20 mL Et₂O in a pre-dried Schlenk tube undernitrogen. At −60° C., the ligand solution was treated dropwise by nBuLi(1.26 mL, 1.6 M in hexanes) via gas-tight syringe. After the temperaturenaturally rose to room temperature, the stirring was continued foranother 4 h. TiCl₄ (1.0 mmol 0.1898 g) in 15 mL Et₂O and 4 mL toluene inanother Schlenk tube was cooled down to −60° C. under nitrogen, intowhich the lithium salt solution of the ligand was dropwise cannulatedin. After completion of the addition, stirring was continued whilenaturally increasing to room temperature. The reaction was furtherstirred for another 16 h before it was filtered through Celite undernitrogen. The volatile was removed under vacuum, obtaining a deep redfine powder, which was purified via recrystallization in benzene/hexanesat −20° C., affording red plate crystals of complex A (0.672 g, 92%). Insolution, two diastereomers were present, with a C₂-symmetric speciespredominating over a C₁-symmetric isomer. ¹H NMR (C₆D₆): δ 1.15 (s,C(CH)₃)₃), 1.20 (s, C(CH₃)₃), 1.42 (s, C(CH₃)₃), 1.60 (s, C(CH₃)₃), 1.83(s, C(CH₃)₃), 6.52-6.89 (m, Ar), 6.90-7.15 (m, Ar), 7.43 (s, Ar),7.48-7.76 (m, Ar). Crystal data (solid state structure): orthorhombic,a=16.2388(13) Å, b=16.7857(13) Å, c=18.0213(14) Å, α=β=γ=90°,V=4912.2(7) Å³, space group p2₁2₁2₁; Z=4, formula weight=891.87 forC₅₄H₆₄Cl₂N₂O₂Ti, and density (calc.)=1.206 g/cm³; R(F)=0.033 andR_(w)(F)=0.083 (I>2σ(I))

EXAMPLE II Synthesis of Complex B

[0051] To a 250-mL Schlenk tube were added 20 mL of methanol 2.3434 g(10 mmol) of 3,5-di-tert-butylsalicylaldehyde, and 1.4924 g (10 mmol) of4-tert-butylaniline. The solution was heated under reflux for 10 hours,followed by reduction of the solvent volume under vacuum Crystallizationat −20° C. afforded pale yellow crystals of Ligand B (2.81 g, 77%). ¹HNMR (CDCl₃): δ 1.35 (s, C(CH₃)₃), 1.37 (s, C(CH₃)₃), 1.48 (s, C(CH₃)₃),7.20-7.25 (m, Ar), 7.40-7.47 (m, Ar), 8.65 (s, CH). In a Schlenk tubeunder nitrogen, 1.462 g (4 mmol) of Ligand B was dissolved in 20 mL ofdiethyl ether. The solution was cooled to −60° C. and 2.5 mL (4 mmol) ofn-butyllithium (1.6 M in hexane) was added dropwise via gastightsyringe. After warming to room temperature, stirring was continued for 4hours. This solution was added dropwise via cannula to a second Schlenktube containing a solution of TiCl₄ (0.219 mL, 2 mmol) in ether (15 mL)and toluene (4 mL) at −60° C. The reaction mixture was stirred at roomtemperature for 16 hours and the solvent was removed under vacuumResidues were redisolved in methylene chloride and filtered throughCelite. The solvent was removed once again, and the crude product wasrecrystallized in benzene/hexanes at −20° C. Red-brown crystals ofComplex B were obtained (1.28 g, 70%). In solution, two diastereomerswere present, with a C₂-symmetric species predominating over aC₁-symmetric isomer. ¹H NMR (CDCl₃): δ 1.11 (s, C(CH₃)₃), 1.23 (s,C(CH₃)₃), 1.26-1.30 (m, C(CH₃)₃), C₁ isomer), 1.34 (s, C(CH₃)₃),6.95-7.10 (m, Ar), 7.12-7.20 (m, Ar, C₁ isomer), 7.34 (s, Ar), 7.40 (d,Ar), 8.04 (s, CH).

EXAMPLE III Synthesis of Complex C

[0052] To a 250-mL Schlenk tube were added 20 mL of methanol, 2.3434 g(10 mmol) of 3,5-di-tert-butylsalicylaldehyde, and 0.099 g (10 mmol) ofcyclohexylamine. The solution was heated under reflux for 10 hours,followed by reduction of the solvent volume under vacuum.Crystallization at −20° C. afforded bright yellow crystals of Ligand C(2.65 g, 84%). ¹H NMR (CDCl₃): δ 1.31 (s, C(CH₃)₃), 1.32-1.40 (m, Cy),1.44 (s, C(CH₃)₃), 1.50-1.90 (m, Cy), 3.20 (m, Cy), 7.15 (d, Ar), 7.37(d, Ar), 8.38 (s, CH). In a Schlenk tube under nitrogen, 1.262 g (4mmol) of Ligand C was dissolved in 20 mL of diethyl ether. The solutionwas cooled to −60° C. and 2.5 mL (4 mmol) of n-butyllithium (1.6 M inhexane) was added dropwise via gastight syringe. After warming to roomtemperature, stirring was continued for 4 hours. This solution was addeddropwise via cannula to a second Schlenk tube containing a solution ofTiCi₄ (0.219 mL, 2 mmol) in ether (15 mL) and toluene (4 mL) at −60° C.The reaction mixture was stirred at room temperature for 16 hours andthe solvent was removed under vacuum. Residues were redisolved inmethylene chloride and filtered through Celite. The solvent was removedonce again, and the crude product was recrystallized in methylenechloride/hexanes at −20° C. Red-brown crystals of Complex C wereobtained (0.60 g, 79%). In solution, two diastereomers were present,with a C₂-symmetric species predominating over a C₁-symmetric isomer. ¹HNMR (CDCl₃): δ 1.11-1.20 (m, Cy), 1.30 (s, C(CH₃)₃), 1.43-1.54 (m, Cy),3.90 (m, Cy), 7.12 (d, Ar), 7.14 (d, Ar, C₁ isomer), 7.42 (d, Ar, C₁isomer), 7.53 (d, Ar, C₁ isomer), 7.58 (d, Ar), 8.12 (s, CH), 8.54 (s,CH, C₁ isomer).

EXAMPLE IV Synthesis of Complex D

[0053] To a 250-mL Schlenk tube were added 20 mL of methanol, 1.492 g(6.36 mmol) of 3,5-di-tert-butylsalicylaldehyde, and 0.708 g (6.36 mmol)of 2-fluoroaniline. The solution was heated under reflux for 10 hours,followed by reduction of the solvent volume under vacuum.Crystallization at −20° C. afforded orange crystals of Ligand D (1.74 g,83%). ¹H NMR (CDCl₃): δ 1.31 (s, C(CH₃)₃), 1.47 (s, C(CH₃)₃), 7.12-7.27(m, Ar), 7.46 (d, Ar), 8.69 (s, CH). ¹⁹F NMR (CDCl₃): δ −6.11 (s). In aSchlenk tube under nitrogen, 0.8583 g (2.62 mmol) of Ligand D wasdissolved in 20 mL of diethyl ether. The solution was cooled to −60° C.and 1.64 mL (2.62 mmol) of n-butyllithium (1.6 M in hexane) was addeddropwise via gastight syringe. After warming to room temperature,stirring was continued for 4 hours. This solution was added dropwise viacannula to a second Schlenk tube containing a solution of TiCl₄ (0.143mL, 1.31 mmol) in ether (15 mL) and toluene (4 mL) at −60° C. Thereaction mixture was stirred at room temperature for 16 hours and thesolvent was removed under vacuum. Residues were redisolved in methylenechloride and filtered through Celite. The solvent was removed onceagain, and the crude product was recrystallized in toluene/hexanes at−20° C. Red-brown crystals of Complex D were obtained (0.388 g, 39%). Insolution, two diastereomers were present, with a C₂-symmetric speciespredominating over a C₁-symmetric isomer. ¹H NMR (CDCl₃): δ 1.20 (s,C(CH₃)₃, C₁ isomer), 1.26 (s, C(CH₃)₃), 1.29 (s, C(CH₃)₃), 6.91 (m, Ar),7.08 (d, Ar), 7.30-7.46 (m, Ar), 7.43 (d, Ar), 8.10 (s, CH), 8.34 (s, CHC₁ isomer). ¹⁹F NMR (CDCl₃): δ 7.22 (d), 10.06 (d).

EXAMPLE V Synthesis of Complex E

[0054] To a Schlenk tube were added 1.7436 g (13.5 mmol) of2,6-difluoroaniline, 1.5824 g (6.75 mmol) of3,5-di-tert-butylsalicylaldehyde, and 4 Å molecular sieves. The solutionwas heated at 120° C. for 18 hours. Crystallization from methanol at−20° C. produced Ligand E as a yellow crystalline solid (1.78 g, 76%).¹H NMR (CDCl₃): δ 1.33 (s, C(CH₃)₃), 1.45 (s, C(CH₃)₃), 6.94-7.05 (m,Ar), 7.06-7.14 (m, Ar), 7.18 (d, Ar), 7.47 (d, Ar), 8.84 (s, CH). ¹⁹FNMR (CDCl₃): δ 9.14 (t). In a Schlenk tube under nitrogen, 0.9584 g(2.77 mmol) of Ligand E was dissolved in 20 mL of diethyl ether. Thesolution was cooled to −60° C. and 1.64 mL (2.62 mmol) of n-butyllithium(1.6 M in hexane) was added dropwise via gastight syringe. After warmingto room temperature, stirring was continued for 4 hours. This solutionwas added dropwise via cannula to a second Schlenk tube containing asolution of TiCl₄ (0.152 mL, 1.39 mmol) in ether (15 mL) and toluene (4mL) at −60° C. The reaction mixture was stirred at room temperature for16 hours and the solvent was removed under vacuum Residues wereredisolved in methylene chloride and filtered through Celite. Thesolvent was removed once again, and the crude product was recrystallizedin toluene/hexanes. Red-brown crystals of Complex E were obtained (0.72g, 64%). ¹H NMR (CDCl₃): δ 1.26 (s, C(CH₃)₃), 1.30 (s, C(CH₃)₃), 6.43(m, Ar), 6.87 (t, Ar), 6.95 (m, Ar), 7.15 (d, Ar), 7.51 (d, Ar), 8.19(s, CH). ¹⁹F NMR (CDCl₃): δ 13.78 (s), 16.81 (s).

EXAMPLE VI Synthesis of Complex F

[0055] N-sulfinyl-2,4,6-trifluoroaniline was prepared by refluxing2,4,6-trifluoroaniline in thionyl chloride. Excess SOCl₂ was removed bydistillation. To a Schlenk tube were added 25 mL of benzene, 1.386 g(5.91 mmol) 3,5-di-tert-butylsalicylaldehyde, and 1.15 g (5.91 mmol) ofN-sulfinyl-2,4,6-trifluoroaniline. This mixture was refluxed undernitrogen for 10 hours. The sulfinyl becomes SO₂ and the driving forcefor the reaction is SO₂. Removal of the solvent and recrystalization inmethanol produced Ligand F as a yellow crystalline solid (1.42 g, 66%).¹H NMR (CDCl₃): δ 1.31 (s, C(CH₃)₃), 1.45 (s, C(CH₃)₃), 6.72-6.80 (m,Ar), 7.16 (d, Ar), 7.47 (d, Ar), 8.81 (s, CH), 13.17 (s, OH). ¹⁹F NMR(CDCl₃): δ −12.63 (t), 8.72 (m). In a Schlenk tube under nitrogen,0.8144 g (2.24 mmol) of Ligand F was dissolved in 20 n of diethyl ether.The solution was cooled to −60° C. and 1.40 mL (2.24 mmol) ofn-butyllithium (1.6 M in hexane) was added dropwise via gastightsyringe. After warming to room temperature, stirring was continued for 4hours. This solution was added dropwise via cannula to a second Schlenktube containing a solution of TiCl₄ (0.123 mL, 1.12 mmol) in ether (15mL) and toluene (4 mL) at −60° C. The reaction mixture was stirred atroom temperature for 16 hours and the solvent was removed under vacuum.Residues were redisolved in methylene chloride and filtered throughCelite. The solvent was removed once again, and the crude product wasrecrystallized in toluene/hexanes. Red-brown crystals of Complex F wereobtained (0.756 g, 80%). ¹H NMR (CDCl₃): δ 1.29 (s, C(CH₃)₃), 1.30 (s,C(CH₃)₃), 6.21 (m, Ar), 6.65 (m, Ar), 7.14 (d, Ar), 7.56 (d, Ar), 8.15(s, CH). ¹⁹F NMR (CDCl₃): δ 58.18 (s), 59.78 (s), 62.63 (p).

EXAMPLE VII Synthesis of Complex G

[0056] N-sulfinylpentafluoroaniline was synthesized by refluxingpentafluoroaniline in excess SOCl₂. N-sulfinylpentafluoroaniline (2.29g, 10 mmol) was then added to 3,5-di-tert-butylsalicylaldehyde (2.34 g,10 mmol) in 20 mL dry benzene under nitrogen, and this solution washeated to reflux for 12 h. Removal of solvent under vacuum gave a yellowsolid that was crystallized from methanol at −20° C., providing ligand Gas a yellow crystalline solid (2.65 g, 66.4%). ¹H NMR (CDCl₃, 300 MHz) δ8.79 (1H, s, CH), 7.52 (1H, d, J=2.4 Hz, ArH), 7.18 (1H, d, J=2.4 Hz,ArH), 1.45 (9H, s, C(CH₃)₃), 1.30 (9H, s, C(CH₃)₃), ¹⁹F NMR (CDCl₃, 400MHz): δ −19.82 (2F, q, J=15 Hz), −26.51 (1F, t, J=21 Hz), −30.16 (2F,m). ¹³C NMR (CDCl₃, 100 MHz): δ 166.2, 154.9, 153.9, 150.5, 136.9,133.5, 125.1, 123.5, 122.2, 114.4, 108.2, 31.4, 30.4, 27.7, 25.64. To astirred solution of ligand G (0.858 g, 2.15 mmol) in diethyl ether (20mL) at −60° C. was added nBuLi (1.34 mL, 1.6 M in hexanes, 2.15 mmol)dropwise using a gas-tight syringe. This solution was allowed to slowlywarm to room temperature and stirred for an additional 4 h. Thissolution was then added dropwise via cannula to a solution of TiCl₄(0.204 g, 1.07 mmol) in diethyl ether (16 mL) and toluene (4 mL) at −78°C. The resulting solution was allowed to warm naturally to roomtemperature and stirred an additional 16 h. After removal of solvent,the residue was taken up in toluene and the precipitated LiCl wasremoved by filtration over a Celite plug. Removal of solvent in vacuogave a deep red powder that was crystallized from a mixture oftoluene/hexane to give the desired complex G as a deep red crystallinesolid (0.702 g, 71% yield). ¹H NMR (CDCl₃, 400 MHz) δ 8.20 (2 H. s, CH),7.66 (2H, d, J=2.4 Hz, ArH), 7.20 (2H, d, J=2.4 Hz, ArH), 1.32 (18 H, s,C(CH₃)₃), 1.30 (18 H, s, C(CH₃)₃), ¹³C NMR (CDCl₃, 100 Mz) δ 198.7,174.0, 160.9, 144.9, 138.2, 134.4, 130.0, 129.2, 128.4, 125.5, 123.6,35.5, 34.7, 31.3, 29.5. Crystal data (solid state structure):orthorhombic, a=16.2248(7) Å b=23.7332(10) Å, c=24.9966(11) Å,α=β=γ=90°, V=9625.4(7) Å³, space group Pbca; Z=8, formula weight=993.68for C₄₂H₄₂Cl₂F₁₀N₂O₂Ti.C₆H₆, and density (calc.)=1.371 g/cm³; R(F)=0.047and R_(w)(F)=0.114 (I>2σ(I)).

EXAMPLE VIII Synthesis of Complex H

[0057] To a Schlenk tube were added 0.9259 g (7.17 mmol) of3,5-difluoroaniline, 1.6806 g (7.17 mmol) of3,5-di-tert-butylsalicylaldehyde, and 4 Å molecular sieves. The solutionwas heated at 120° C. for 18 hours. Crystallization from methanol at−20° C. produced Ligand H as a brown crystalline solid (1.99 g, 80%). ¹HNMR (CDCl₃): δ 1.31 (s, C(CH₃)₃), 1.46 (s, C(CH₃)₃), 6.68-6.73 (m, Ar),6.79-6.82 (m, Ar), 7.22 (d, Ar), 7.48 (d, Ar), 8.60 (s, CH), 13.14 (s,OH). ⁹F NMR (CDCl₃): δ −23.40 (t). In a Schlenk tube under nitrogen,1.1386 g (3.29 mmol) of Ligand H was dissolved in 20 mL of diethylether. The solution was cooled to −60° C. and 2.06 mL (3.29 mmol) ofn-butyllithium (1.6 M in hexane) was added dropwise via gastightsyringe. After warming to room temperature, stirring was continued for 4hours. This solution was added dropwise via cannula to a second Schlenktube containing a solution of TiCl₄ (0.181 mL, 1.65 mmol) in ether (15mL) and toluene (4 mL) at −60° C. The reaction mixture was stirred atroom temperature for 16 hours and the solvent was removed under vacuum.Residues were redisolved in methylene chloride and filtered throughCelite. The solvent was removed once again, and the crude product wasrecrystallized in toluene/hexanes. Red-brown crystals of Complex H wereobtained (0.74 g, 55%). In solution, two diastereomers were present,with a C₂-symmetric species predominating over a C₁-symmetric isomer. ¹HNMR (CDCl₃): δ 1.26 (s, C(CH₃)₃), 1.29 (s, C(CH₃)₃), C₁ isomer), 1.30(s, C(CH₃)₃, C₁ isomer), 1.36 (s, C(CH₃)₃), 6.29 (m, Ar), 6.42 (m, Ar),6.53 (m, Ar), 6.64-6.69 (m, Ar, C₁ isomer), 6.73-6.77 (m Ar, C₁ isomer),7.11 (d, Ar), 7.15 (m, Ar, C₁ isomer), 7.53 (d, Ar), 7.62 (d, Ar, C₁isomer), 7.68 (d, Ar, C₁ isomer), 7.99 (s, CH, C₁ isomer), 8.03 (s, CH,C₁ isomer), 8.08 (s, CH). ¹⁹F NMR (CDCl₃): δ 22.94 (s), 23.96 (s), 24.99(t).

EXAMPLE IX Synthesis of Complex I

[0058] To a 250-mL Schlenk tube were added 20 mL of methanol, 1.7823 g(10 mmol) of 3-tert-butylsalicylaldehyde, and 0.93 g (10 mmol) ofaniline. The solution was heated under reflux for 10 hours, followed byreduction of the solvent volume under vacuum. Crystallization at −20° C.afforded orange-yellow crystals of Ligand I ( 2.23 g, 88%). ¹H NMR(CDCl₃): δ 1.45 (s, C(CH₃)₃), 6.80 (t, Ar), 7.12 (m, Ar), 7.40 (m, Ar),8.60 (s, CH). In a Schlenk tube under nitrogen, 1.013 g (4 mmol) ofLigand I was dissolved in 20 mL of diethyl ether. The solution wascooled to −60° C. and 2.5 mL (4 mmol) of n-butyllithium (1.6 M inhexane) was added dropwise via gastight syringe. After warming to roomtemperature, stirring was continued for 4 hours. This solution was addeddropwise via cannula to a second Schlenk tube containing a solution ofTiCl₄ (0.219 mL, 2 mmol) in ether (15 mL) and toluene (4 mL) at −60° C.The reaction mixture was stirred at room temperature for 16 hours andthe solvent was removed under vacuum. Residues were redisolved inmethylene chloride and filtered through Celite. The solvent was removedonce again, and the crude product was recrystallized in benzene/hexanesat −20° C. Red-brown crystals of Complex I were obtained (1.08 g, 78%).In solution, two diastereomers were present, with a C₂-symmetric speciespredominating over a C₁-symmetric isomer. ¹H NMR (CDCl₃): δ 1.34 (s,C(CH₃)₃), 6.74-6.84 (m, Ar), 6.98-7.30 (m, Ar), 7.40-7.43 (m, Ar),7.54-7.63 (m, Ar), 7.91 (s, CH, C₁ isomer), 8.04 (s, CH, C₁ isomer),8.06 (s, CH).

EXAMPLE X Preparation of Syndiotactic Polypropylene and of BlockCopolymers Containing Syndiotactic Polypropylene Blocks

[0059] The following general procedure was used for preparation ofsyndiotactic polypropylene: A 6 oz Lab-Crest® pressure reaction vessel(Andrews Glass) equipped with a magnetic stir bar was first conditionedunder dynamic vacuum (20 mTorr) and high temperature (200° C.) and thencharged with a desired amount of PMAO and toluene (150 mL). The reactorwas the equilibrated at 0° C. in an ice bath. At this point, the reactoratmosphere was exchanged with propylene gas three times, and then thesolution was saturated with propylene under pressure (40 psi). Therequired amount of the titanium catalyst was dissolved in toluene (8 mL)at RT under nitrogen, and the solution was added to the reactor viagas-tight syringe to initiate the polymerization. After the desiredperiod of time, the reactor was vented. The polymer was precipitated incopious methanol/HCl, filtered, washed with methanol and then dried invacuo to constant weight.

[0060] The following procedure was used for preparation ofsyndio-propylene-block-poly(ethylene-co-propylene): A 6 oz Lab-Crest®pressure reaction vessel (Andrews Glass) equipped with a magnetic stirbar was first conditioned under dynamic vacuum (20 mTorr) and hightemperature (200° C.) and then charged with PMAO (15 mmol) and toluene(150 mL). The reactor was cooled to 0° C., and the atmosphere wasexchanged with propylene gas three times, and then saturated withpropylene under pressure (40 psi). A solution of titanium complex (0.10mmol) in toluene (6 mL) was then added to the reactor via gas-tightsyringe to initiate the polymerization. After the initial propylenepolymerization, a 5-mL sample was removed via gas-tight syringe, andethylene at 5 psi overpressure was introduced into the reactor. After 1hour of additional polymerization time, the reaction was quenched byinjection of methanol/HCl (2 mL, 10% vol HCl). After venting thereactor, the polymer was precipitated in copious methanol/HCl, filtered,washed with methanol, and then dried in vacuo to constant weight.

[0061] The following general procedure was used for preparation ofsyndio-polypropylene-block-poly(ethylene-co-propylene)-block-syndio-propylene:A 6 oz Lab-Crest® pressure reaction vessel (Andrews Glass) equipped witha magnetic stir bar was first conditioned under dynamic vacuum (20mTorr) and high temperature (200° C.) and then, charged with PMAO (15mmol) and toluene (150 mL). The reactor was cooled to 0° C., and theatmosphere was exchanged with propylene gas three times, and thensaturated with propylene under pressure (40 psi). A solution of titaniumcomplex (0.10 mmol) in toluene (6 mL) was then added to the reactor viagas-tight syringe to initiate the polymerization. After the initialpropylene polymerization, a 5-mL sample was removed via gas-tightsyringe, and ethylene at 5 psi overpressure was introduced into thereactor. After the reaction times as stated in Table II hereinafter ofadditional polymerization time, a sample was removed for analysis andthe ethylene source was shut off. The reaction quickly consumed theresidual ethylene and reverted to propylene polymerization for thedesired amount of time. Then the reaction was quenched by injection ofmethanol/HCl (2 mL, 10% vol HCl). After venting the reactor, the polymerwas precipitated in copious methanol 10% HCl, filtered, washed withmethanol, and then dried in vacuo to constant weight.

[0062] Other reaction conditions and results are given in Table II belowand in the footnotes thereto. In Table II, “rxn” means reaction, P meanspropylene, and E means ethylene. The MAO used was PMAO. TABLE II^(a) Rxntime T_(rxn) Yield Complex (h) (° C.) Monomer (g) Activity^(b) M_(n)^(c) M_(w)/M_(n) ^(c) [rrrr] A 24 0 P 4.20 1.75  9,910 2.14 0.78 B 24 0P 3.62 1.51  16,943 1.44 0.87 C 24 0 P 3.70 1.54  8,850 1.59 0.73 D 24 0P 0.38 0.16  3,010 1.07 0.52 E 24 0 P 0.56 0.23  15,487 1.06 0.83 F 24 0P 2.48 1.03  40,208 1.08 0.95 G  0.25 0 P 0.49 19.6  11,100 1.09 0.96 G 0.50 0 P 0.97 19.4  24,500 1.08 0.96 G  1.5 0 P 1.79 11.9  44,700 1.110.96 G  3.1 0 P 3.84 12.4  75,800 1.08 0.96 G  5.2 0 P 5.34 10.3  95,9001.11 0.96 G 66^(d) 0 P 14.2 2.15 307,700 1.34 0.96 G 24 20 P 7.43 3.09102,500^(e)  1.13^(e) 0.96 H 24 0 P 23.4 9.75  13,584 1.91 0.81 I 24 0 P3.00 1.25  5,000 2.59 0.79 G 2.0/1.0^(f) 0 P/E 11.2 NA  38,400/  1.11/0.96 145,100^(g)  1.12^(g) G 2.0/0.33/ 0 P/E/P NA NA  30,900/  1.07/ 0.96^(l) 2.0^(h)  44,200/  1.08/  70,300^(i)  1.08^(i) G 2.0/1.0/ 0P/E/P NA NA  38,000/  1.06/  0.96^(l) 2.0^(j) 169,000/  1.09/189,000^(i)  1.13^(i) G 2.0/0.50/ 0 P/E/P NA NA  36,000/  1.11/ 0.96^(l) 3.0^(k) 217,000/  1.11/ 260,000^(i)  1.18^(i)

[0063] In Table II, the first 15 entries represent preparation ofsyndiotactic polypropylene, the sixteenth entry represents preparationof SPP-EP diblock and the seventeenth, eighteenth and nineteenth entriesrepresent preparation of SPP-EP-SPP triblock. The entries in Table IIwhere complexes A, H and I were used provide olefin terminated product.The product for the entry for Complex H has the formula (II) wheren=323.

[0064] SPP-EP-SPP-EP-SPP pentablock is formed when the procedure offootnote k to Table II is modified to propylene homopolymerization forthe third block to 2 hours whereupon a 5 psi overpressure of ethylene isadded for 30 minutes whereupon ethylene flow is terminated and reactionis allowed to return to propylene homopolymerization for 2 hours.

[0065] Poly(propylene)-block-poly(l-butene-co-propylene) diblock polymeris formed when the procedure for note f to Table II, is modified tosubstitute an overpressure of 1-butene for 1 hour for the overpressureof ethylene.

EXAMPLE XI

[0066] The following procedure is used for the preparation ofsyndiotactic poly(1-butene). A 6 oz Lab-Crest® pressure vessel (AndrewsGlass) equipped with a magnetic stir bar is first conditioned underdynamic vacuum and high temperature and then charged with 15 mmol PMAOand toluene (150 ml). The reactor is equilibrated at 0° C. in an icebath. At this point, 10 ml of 1-butene is added. Then 0.1 mmol complex Gis dissolved in toluene (8 ml) at RT under nitrogen, and the solution isadded to the reactor via gas-tight syringe to initiate thepolymerization. After 12 hours, the reactor is vented. The polymer isprecipitated in copious methanol/HCl, filtered, washed with methanol anddried in vacuo to constant weight. The poly(1-butene) product has M_(n)of about 60,000, M_(w)/M_(n) of about 1.15 and [rrrr] of about 0.95.

[0067] Variations

[0068] Many variation will be obvious to those skilled in the art.Therefore, the invention is defined by the claims.

1-10. (Canceled)
 11. Syndiotactic poly(C₄-C₆-alpha olefin) having aM_(w) ranging from 10,000 to 500,000 and M_(w)/M_(n) ranging from 1.0 to2.0.
 12. A method of preparing syndiotactic polypropylene having M_(w)ranging from 10,000 to 500,000 and defects of the type rmr and [rmr]pentad content greater than 0.50 comprising polymerizing propylenedissolved in an aprotic solvent in the presence of a catalyticallyeffective amount of a complex having the structure:

where R is selected from the group consisting of halogen atoms, C₁-C₁₀branched or straight chain alkyl groups, C₁-C₆ branched or straightchain alkoxide groups, and C₁-C₆ branched or straight chain amidogroups, R₁ is phenyl or cyclohexyl optionally substituted with one tofive C₁-C₆ branched or straight chain alkyl groups or one to fiveelectron withdrawing atoms or groups, or is C₁-C₁₀ branched, cyclic orstraight chain alkyl group, and R₂ and R₃ are the same or different andare selected from the group consisting of H or C₁-C₆ branched orstraight chain alkyl groups and an activating effective amount ofcompound that converts titanium of the complex to cationic form.
 13. Themethod of claim 12 where the compound that converts titanium of thecomplex to cationic form is an aluminum-containing compound.
 14. Olefinterminated polymers and oligomers of propylene having the structure:

where n ranges from 1 to
 750. 15. A method of preparing polymers andoligomers of propylene having the structure (II) where n ranges from 1to 750, comprising polymerizing propylene in an aprotic solvent in thepresence of a catalytically effective amount of complex having thestructure (I) where R is selected from the group consisting of halogenatoms, C₁-C₁₀ branched or straight chain alkyl groups, C₁-C₆ branched orstraight chain alkoxide groups, and C₁-C₆ branched or straight chainamidio groups, R₁ is phenyl optionally substituted at one or more of the3-, 4-, and 5-positions but not at the 2 and 6-positions, the optionalsubstitution at one or more of the 3-, 4-, and 5-positions being withC₁-C₆ branched or straight chain alkyl group or electron withdrawingatom or group, and R₂ and R₃ are the same or different and are selectedfrom the group consisting of H and C₁-C₆ branched or straight chainalkyl groups and an activating effective amount of compound thatconverts titanium of the complex to cationic form. 16-22. (Canceled)